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Fluorine Segregation Controls the Solid-State Organization and Electronic Properties of Ni and Au Dithiolene Complexes: Stabilization of a Conducting Single-Component Gold Dithiolene Complex
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2002
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EngineeringTheoretical Inorganic ChemistryFluorine SegregationFluorous BilayersElectronic PropertiesChemistryInorganic CompoundMaterials ScienceInorganic ChemistryNanotechnologyAu Dithiolene ComplexesMetallic ConductivityElectrochemistryTransition Metal ChalcogenidesElectronic MaterialsNanomaterialsLayered StructureMolecule-based MaterialFunctional Materials
Electrooxidation of the nickel dithiolene complex [Ni(F2pdt)2]–· (F2pdt2-: 6,6-difluoro-6,7-dihydro-5H-[1,4]dithiepine-2,3-dithiolato) affords the corresponding neutral complex [Ni(F2pdt)2]0 whose layered structure is highly reminiscent, albeit not isostructural, of that of the isosteric fluorinated bis(propylenedithio)tetrathiafulvalene and characterized by a segregation of the fluorinated moieties into fluorous bilayers. The gold neutral complex [Au(F2pdt)2]·, which is isostructural with the fluorinated bis(propylenedithio)tetrathiafulvalene, was prepared by electrocrystallization of the [n-Bu4N][Au(F2pdt)2] salt. [Au(F2-pdt)2]· is a semiconductor with high room temperature conductivity. The origin of this semiconducting behavior as well as possible guidelines in order to realize metallic conductivity in gold dithiolene neutral molecular solids are discussed.